Process for the making of medicinal oil



July 9, 1935. B. E. CARL PROCESS FOR THE- MAKING OF MEDICINAL OIL Filed Feb. 25, 1952 2 Sheets-Sheet 1 NVENToR ML July 9, 1935.l B. E. CARL PROCESS FOR lTHE MAKING OF MEDICINAL OIL 2 Sheets-Sheet 2 Filed Feb. 25, 1952 A'I'I'O NEY Patented July 9, `1935 UNITED STATES,

PaocEss Foa THE MAKING o MEDICINALOIL Y Byron E. Carl, New York, N. Y., assigner of onethird to Clarence N. Y.

G.l Campbell, PelhamkManor,

.fiaplirati'orrV February ze, 1932, serial No. 594,528 Y Claims. (Cl. 1943-40) consists in the steps of said process as will b more fully hereinafter pointed out. t

There are many unsatised commercial demands for an absolutely pure mineral oil devoid of taste, odor, color and unsaturated constituents and possessing a high degree of stability under the influence of air, light andheat and particularlyl for medicinal use. has not been solved because of the abstruse chemical problems involved and the mineral oil now used for medicinal purposes lacks many of these essential requirements. Y

My process for the first time solves this problem andproduces a mineral oil having all of the above described required qualities for medicinal use.

`One of the objects of the present invention iis the production of hydrocarbon oils suitable for medicinal and technical purposes devoid of taste, odor, color and of unsaturated constituents and possessing a high degree of stability under the iniiuence of air, light and heat, byrepeated treatment of a suitable raw material with a metallic halide, preferably anhydrous and active aluminum-chloride. v

A further object of this invention is the application ci' a mechanical beating, cutting and tearing Adevice with whichappropriate and highly eiiicient intimate contacting of the oil with the metal halide can be effected.

It is known that metallic halides, in particular Al C13, react with crude hydrocarbon oils in a variety of ways. `Atlower temperature the action of the Al C13 Yconsists mainly in the removal of impurities, such as sulphur and nitrogencompounds, in the conversion of hydrocarbonaceous constituents of an unsaturated nature to the corresponding products of saturation and further in the formation of hydrocarbon compounds of higher molecular weight, i. e. by polymerization. The reverse action, i. `e. the conversion of higher molecular hydrocarbons to such of lower molecular weight, although not completely avoidable takes place but .to la very small degree when the treatment with the halide is effected at atmospheric temperatures or belo-w. Y

Besides working at atmospheric temperatures or below the action of the metal halide on the raw hydrocarbons can also be kept under closer control, as is so often the Ycase in chemical processes, by working in dilute solution and,- ii so desired, by the application of artificial cooling i. e. dissipation of the whole or a part of the heatformed in the reaction and by friction of the apparatus with 'the' oil being treated by any of the well known and accepted means vsuch as by external cooling during the intimate; contact- But this problem ing of theoil and aluminum chloride and the tearing apart of the same. Straight run crude oil naphtha, pretreated with a small percentage of concentrated sulphuric acid in order to avoid dissipation oi any part of the metal halide and of known boiling range may very well serve as a .diluenh Besides the difculties in the chemical treatment of crude hydrocarbon oils with metal halvides, especially with Al C13, as a result of the multiplicity in the nature invvhich this latter agent can react with the former there exists also a number of diiiicultiesrof a purely mechanical nature in effecting really eflicient contact between the halide and the oil. Owing to the low fluidity of the oil and that of the sticky, tarry Al Cla sludge formed in the reaction and which latter tends to "occlude considerable portions of unconsumed chloride, only a part of the chloride employed `becomes effective and further, since the difference in the` specic gravities of the oil and the sludge tar is, relatively taken, very small, there exists also a tendency of the latter to'form fairly stable emulsions with the former. Vari- Vous means have been' recommended to eect a `thorough mixing of `the chloride with the oil.

Violent agitation of the oil and chloride mixtures with mechanical stirrers as is customary to employ in carrying out chemical reactions have proven to be of littleavail since such devices effect solely a rotative movement of the body of oil carrying the chloride in suspension, but, as previously mentioned, a considerable part of the chloride rapidly becomes enclosed in the sludge andthereby loses its effectiveness, which results in a loss, i. e. undue'waste in chloride and oil. Eicient contacting therefore, can only then be attained when besides a thorough mixing of the chloride and oil also a breaking up of the agglomerations of the sludge and particles of unused chloride is effected, this resulting in a reexposure of the occluded but still active chloride;V This greatly desired result can be secured eifectively and efficiently with the following described mechanism.

Referring to the drawings Figure 1 is a side elevation of my device With a portion broken away` to showrthe interior and broken forconvenience in illustration.

Figure 2 is a cross section of one of the arms of a cutting, tearing and beating member.

Figure 3 is a side elevation of one of said cutting', tearing and beating members. l

Figure 4 is a top plan view of Figure 3.

.Figure 5 is a sectional'elevation of Figure 1 on the line 5 5. i

Figure 6 is a front elevation of Figure l with side portions Vbroken away for convenience in' illustration.

inthe drawings 1 is .a long cynndricaitank rigidly supported on the usual standards 8 and having end members 9 and I0 of usual construction rigidly secured thereto, 9 being rigidly secured at 9a and I0 removably secured by clamps Illa. On the interior of the tank 'I are rigidly mounted longitudinally of the tank U-shaped tracks I I on each side and at the top of the tank and a longitudinal U-shaped groove I2 along the bottom of said tank serves the same purpose as I I. v

A pair of rotating shafts I3 and I4 run the entire length of said tank 1 and are supported at the inner end on the usual bearings I5 and I6 and extend into the openings II in the end member I 8 which is rigidly secured to said end 9. Supporting frame members are mounted over the said shafts I3 and I4 and have roller members 35 at the ends of each of the frame arms adapted to travel in the tracks II and I2. Cutting, tearing and beating members 20 having beveled sides 2| and cutting edges 22 are mounted rigidly on said shafts I3 and I4 on either side of the frame members I9 by means of the sleeve members 23 and set screws 24.

A cut gear 25 is rigidly secured to the outer end of shaft I3 and is adapted to be meshed and driven by a gear from a shaft driven from a source of power, all of which is not shown herein. A cut gear 33 is rigidly secured to shaft I3 and is adapted to mesh with gear 34 rigidly secured t0 shaft I4 so as to drive the same.

A car 26 runs on tracks 21 on wheels 29 and is secured at 28 to the end I0 and by chains 30 is secured at 3| to the front of said car 26 and at 32 is secured to the front I 8 in the usual manner.

In operating my device as the outside power driven shaft through gear (not shown) meshed with gear 25 is set in operation shaft I3 is operated and through gears 33 and 34 shaft I4 is also operated simultaneously in the opposite direction. The cutting, tearing and beating members 20 rigidly secured to said shafts I3 and I4 are thereby rotated in opposite directions on said two shafts so as to cut up, tear apart and beat the oil and aluminum chloride placed in tank 1 for treatment as described herein.

Whenever it is desired to clean or get into said tank I for any reason the clamps I0a are unfastened and by pulling on the car 26 and drawing it out on tracks 2T the end I0 is pulled out with it and the shafts I3 and I4 and the beating, tearing, cutting members 20 mounted thereon and the frame members I9 mounted between said members 20 on said shafts I3 and I4 will travel therewith, supporting all on the wheels 35 in the tracks ll and 12.

The tank '7 also has a drain pipe 3`I with the usual control valve. A feed or inlet pipe 38 with the usual control valve is also connected to the tank I and a further feeding pipe 39 with the usual type of funnel is connected to the tank 'I so that by means of pipes 38 and 39 the oil, aluminum chloride and other material to be used in the process described can be placed in the tank 1 as desired and the treated material drawn off either in sludge or in the resulting product of the operation through the pipe 3T. 40 is an elliptical protective flange rigidly secured to the front of the end member I0.

Another difficulty in the efficient treating of hydrocarbon oils with Al C13 is encountered in the clean separation of the treated oil and the Al C13 sludge, since as a rule, a more or less considerable part ofthe sludge remains in a ne suspension in the oil and settles out but very slowly. if at all` This difficulty can easily be overcome by agitation of the treated oil after removal of the bulk of the Al C13 sludge with a small percentage, say one to two percent by weight of H2 S04 of 60 Baume prior to the treatment with a new batch of chloride. After application of several Al Cla dumps the washing of the oil with 60 Baume acid after each or every second treatment can be dispensed with, since after removal of the bulk of the unsaturated constituents contained in the original oil with the preceding Al C13 treatments the sludge shows an increasing tendency to agglomerate to large chunks leaving the oil practically clear, or faintly opalescent.

In the dyeing of animal fibre, for instance wool, it is common practice to accelerate the wetting of the fibre by means of a wetting agent which is applied in quantities of one-half to one percent by weight of the fibre. The addition of the wetting agent tends to reduce surface tension between the fibre and the bath, which results in a rapid soaking of the liquid into the fibre, i. e. a rapid becoming wet of the latter. An analogous effect is obtained when adding a small quantity of a wetting agent to the oil, Al C13 and sludge mixture prior to the termination of the treatment. The surface tension of the sludge particles is substantially reduced so the agglomeration of these latter is accelerated. The addition of the wetting agents is more beneiicious in the first treatments with Al C13 portions than in the final ones. As a wetting agent any one of those used in the textile industry can be employed, such for example as benzolbutanolsulphuric acid.

If the production of absolutely odorless and tasteless medicinal oils possessing a very low iodine number and complying rigorously with the specifications of the U. S. Pharmacopia is aimed at, it is necessary to subject the Al C13 treated oils to a more or less drastic treatment with concentrated, or better, fuming sulphuric acid prior to the washing and the percolation of the oil through clay or other decolorizers. The procedure is as follows: After exhaustive treatment of the oil with Al C12 the last traces of the latter are removed by washing with one to two per cent by weight of 60 Baume sulphuric acid whereupon the oil is treated with one-half to one pound per gallon of commercial fuming acid applied in one or more dumps. After settling and removal of the acid sludge the oil is washed first with one to two percent by weight of 60 Baume acid, then with three to four percent by volume of acid of thirty to thirty-five percent, followed by a wash with twenty to thirty percent volume of dilute acid l-l0 or one-tenth normal strength. After removal of the dilute acid the oil is given a wash with one-fourth to onethird of its volume of 'water to which a small percentage, five to ten percent, of a commercial appropriately denatured alcohol is added. This alcohol'wash is then followed by one or several washes with pure Water until the point of neutrality has been practically reached. The oil is then clarified by warming with closed steam to around 200 F. and settling.

'I'he clarified oil is then percolated hot through dried clay or suitable mesh and the decolorized oil transferred to a still in which the diluent is removed by distillation with fire and steam, or, if so desired, under reduced pressure.

The reduced oil is then withdrawn from the still, contacted hot with dried fine clay of eight t0 ten pounds per barrel of oil and filtered. The

accasion product thus obtained representing an oil suitable for use as a medicinal oil.

The process as set forth with the above is applicable to raw materials of any description which have, or have not undergone pretreatfments for the purpose of removing resinous and asphaltic compounds, impurities such as sulphur or nitrogen compounds and solid hydrocarbons compounds by means of the various known de- Waxing methods.

From raw materials of a paraflinic nature the solid hydrocarbons can be separated subsequent to the treatment with the metal halide or/and rto the nishing treatments with concentrated H2 S04 or fuming acid.

I claim: Y

1. A process for the making of medicinal oil from hydrocarbon oil comprising the intimate contacting of said hydrocarbon oil with continuously torn apart and reexposed active aluminum chloride at atmospheric temperature, removing the sludge formed by said reaction, washing the treated oil with one to two percent by weight of 60 Baume sulphuric acid, treating the said oil with one-half to one pound per gallon oi commercial fuming sulphuric acid, washing the said oil with one to two percent by weight of 60 Baume sulphuric acid, further washing said oil with three to four percent by volume of to Baume sulphuric acid, further washing said oil with twenty to thirty percent by volume of dilute sulphuric acid Y washing said oil by one-fourth to one-third of its volume with water, washing said oil with distilled water until point of neutrality has been practically reached, the oil is then claried by warming to around 200 F. and settled, the clarified oil is then percolated hot through dried clay of suitable mesh, the treated oil is then distilled and the reduced oil is then contacted hot with dried ne clay and filtered.

2. A process for the making of medicinal oil from hydrocarbon oil comprising diluting the oil to be treated with untreated straight run naphtha, the intimate contacting and continuously tearing apart and reexposing of active aluminum chloride with said hydrocarbon oil at atmospheric temperature, removing the sludge formed by said reaction, washing the treated oil with one to two percent by weight of 60 Baume sulphuric acid, treating the said oil -with one-half to one pound per gallon of commercial fuming sulphuric acid, washing the said oil with one to two` percent by weight of 60 Baume sulphuric acid, further washing said oil with three to four percent by volume of 30 to 35 Baum sulphuric acid, further washing said oil with twenty to thirty percent by volume of dilute sulphuric acid washing said oil by one-fourth to one-third of its volume with water, washing said oil with distilled water until point of neutrality has been practically reached, the oil is then claried by warming to around 200 F. and settled, the claried oil is then percolated hot through dried clay ofcsuitable mesh, the treated oil is then distilled and the reduced oil is then contacted hot with dried fine clay and filtered. l

3. A process for the making of medicinal oil from hydrocarbon oil comprising diluting the oil to be treated with treated straight run naphtha, the intimate contacting of said hydrocarbon oil with active and continuously torn apart and reexposed aluminum chloride at atmospheric temperature, removing the sludge formed by said reaction, washing the treated oil with one to two percent by weight of 60 Baume sulphuric acid, treating the said oil with one-half to one pound per gallon of commercial fuming sulphuric acid, Washing the said oil with one to two percent by weight of 60 Baume sulphuric acid, further washing said oil with three to four percent by volume of 30 to 35 Baume sulphuric acid, further washing said oil with twenty to thirty percent by volume of dilute sulphuric acid washing said oil by one-fourth to one-third of its volume with water, washing said oil with distilled water until point of neutrality has been practically reached, the oil is then clarified by warming to around 200 F. and settled, the clarified oil is then percolated hot through dried clay of suitable mesh, the treated oil is then distilled and the reduced oil is then contacted hot with dried line clay and filtered.

4, A process for the making of medicinal oil from hydrocarbon oil comprising the intimate contacting of said hydrocarbon oil with active aluminum chloride and reexposure of the occluded aluminum chloride below atmospheric temperature, removing the sludge formed by said reaction, washing the treated oil with one to two percent by weight of 60 Baume sulphuric acid, treating the said oil with one-half to one pound per gallon of commercial iuming sulphuric acid, washing thel said oil with one to two percent by weight of 60 Baume sulphuric acid, further washing said oil with three to four percent by volume of 30 to 35 Baume sulphuric acid, further washing said oil with twenty to thirty percent by volume of dilute sulphuric acid N 'ib washing said oil by one-ourth to one-third of its volume with water, washing said oil with distilled water until point of neutrality has been practically reached, the oil is then claried by warming to around 200 F. and settled, the claried oil is then percolated hot through dried clay of suitable mesh, the treated oil is then distilled and the reduced oil is then contacted hot with dried fine clay and filtered.

5. A process for the making of medicinal oil from hydrocarbon oil comprising pretreating the raw hydrocarbon oil with a small percentage of concentrated sulphuric acid, the intimate contacting of said hydrocarbon oil with active and continuously torn apart and reexposed aluminum chloride at atmospheric temperature, removingy the sludge formed by said reaction, washing the treated oil with one to two percent by weight of Baume sulphuric acid, treating the said oil v with twenty to thirty percent by volume of dilute sulphuric acid washing said oil by one-fourth to one-third of its volume with water, washing said oil with distilled water until point of neutrality has been practically reached, the oil is then clarified by warming to around 200 F. and settled, the clarified oil is then percolated hot through dried clay of suitable mesh, the treated oil is then distilled and the reduced oil is then contacted hot with dried iine clay and filtered.

6. A process for the making of medicinal oil from hydrocarbon oil comprising the intimate contacting and continued tearing apart and reexposure of the active aluminum chloride with said hydrocarbon oil below atmospheric temperature, removing the sludge formed by said reaction, washing the treated oil with one to two percent by Weight of 60 Baume sulphuric acid, treating the said oil with one-half to one pound per gallon of commercial fuming sulphuric acid, washing the said oil with one to two percent by weight of 60 Baume sulphuric acid, further washing said oil with three to four percent by volume of 30 to 35 Baume' sulphuric acid, further washing said oil with twenty to thirty percent by volume of dilute sulphuric acid washing said oil by one-fourth to one-third of its Volume with water, washing said oil with distilled water until point of neutrality has been practically reached, the oil is then clarified by warming to around 200 F. and settled, the claried oil is then percolated hot through dried clay of suitable mesh, the treated oil is then distilled and the reduced oil is then contacted hot with dried fine clay and ltered.

7. A process for the making of medicinal oil from hydrocarbon oil comprising diluting the oil to be treated with pure crude oil naphtha of known boiling range pretreated with a small percentage of concentrated sulphuric acid in order to avoid dissipation of any part of the metal halide, the intimate contacting of said hydrocarbon oil with active aluminum chloride at atmospheric temperature, removing the sludge formed by said reaction, washing the treated oil with one to two percent by weight of 60 Baume sulphuric acid, treating the said oil with one-half to one pound per gallon of commercial filming sulphuric acid, washing the said oil with one to two percent by weight of 60 Baume sulphuric acid, further Washing said oil with three to four percent by volume of 30 to 35 Baume sulphuric acid, iurther Washing said oil with twenty to thirty percent by volume of dilute sulphuric acid washing said oil by one-fourth to one-third of its volume with water, washing said oil with distilled water until point of neutrality has been practically reached, the oil is then clarified by warming to around 200 F. and settled, the clariiied oil is then percolated hot through dried clay of suitable mesh, the treated oil is then distilled and the reduced oil is then contacted hot with dried fine clay and ltered.

8. A process for the making of white oil from hydrocarbon oil comprising the continuous intimate contacting, tearing apart and reexposure of occluded active aluminum chloride with said hydrocarbon oil below atmospheric temperature, removing the sludge formed by said reaction, washing the treated oil with 60 Baum sulphuric acid, treating the said oil with commercail fuming sulphuric acid, washing the said oil with 60 Baume sulphuric acid, further washing said oil with 30 to 35 Baume sulphuric acid, further `washing said oil with dilute sulphuric acid washing said oil with distilled water until point of neutrality has been practically reached, the oil is then clarified by warming 'to around 200 F. and settled, the clarified oil is then percolated hot through dried clay of suitable mesh, the treated oil is then distilled and the reduced oil is then contacted hot with dried ne clay and ltered.

9. A process for the making of white oil from hydrocarbon oil comprising the continuous intimate contacting and reexposure of occluded and other active aluminum chloride with said hydrocarbon oil at atmospheric temperature, removing the sludge formed by said reaction, washing the treated oil with 60 Baum sulphuric acid, treating the said oil with commercial fuming sulphuric acid, washing the said oil with 60 Baum sulphuic acid, further Washing said oil with 30 to 35 Baume sulphuric acid, further washing said oil with dilute sulphuric acid washing said oil with distilled water until point of neutralityv has been practically reached, -the oil is then clarified by Warming to around 200 F. and settled, the claried oil is then percolated hot through dried clay of suitable mesh, the treated oil is then distilled and the reduced oil is then contacted hot with dried ne clay and filtered. 10. A process for the making of white oil from hydrocarbon oil comprising diluting the oil to be treated with pure crude oil naphtha pretreated with a small percentage of concentrated sulphuric acid in order to avoid dissipation of any part of the metal halide, the continuous intimate contacting and reexposure of occluded and all active aluminum chloride with said hydrocarbon oil below atmospheric temperature, removing the sludge formed by said reaction, washing the treated oil with 60 Baume sulphuric acid, treating the said oil with commercial fuming sulphuric acid, washing the said oil with 60 Baume sulphuric acid, further Washing said oil with 30 to 35 Baume sulphuric acid, further washing said oil with dilute sulphuric acid washing said oil with distilled water until point of neutrality has been practically reached, the oil is then clariied by Warming to around 200 F. and settled, the clariiied oil is then percolated hot through dried clay of suitable mesh, the treated oil is then distilled and the reduced oil is then contacted hot with dried ne clay and filtered.

BYRON E. CARL. 

